Azo-dyestuffs



Patented May 26, 1936 UNITED STATE AZO-DYESTUFFS Joseph Gyr and Otto Kaiser, Basel, Switzerland, assignors to Society of Chemical Industry in Basle, Basel, Switzerland No Drawing.

Application December 10, 1932,

Serial No. 646,707. In Switzerland December In U. S. Patent No. 1,667,312, Example 14, there is described a direct dyeing green polyazo-dyestufi, which can be made by the action of the diazotized azo-dyestufi from 1-diazo-8-hyd1'oxynaphthalene-3:G-disulfonic acid and cresidine on 1 mol. of the ternary condensation product from 1 mol. cyanuric chloride, 1 mol. 1-amino-8-hydroxynaphthalene-3:G-disulfonic acid, 1 mol. 4'- amlno-4-hydroxyazobenzene-3-carboxylic .acid and 1 mol. aniline. This dyestuff is characterized by the beauty and the outstanding fastness to light of the dyeings on cotton which can be obtained by its use. It has, however, the disadvantage that it is sensitive to calcium carbonate, 15 so that when hard water is used "in the dyeing operation enfeebled dyeings may easily be produced.

The present invention relates to green, direct dyeing azo-dyestuffs fast to light which, on the" one hand, are insensible in the dye-bath towards 3 Claims. (Cl. 260-27) l-diazo 8 hydroxynaphthalene 3:6 -disulfonic acid (if desired in the form of an O-acyl ester) and a middle component of the general formula 1/ (in which y and x represent akyl or alkoxy), 1 mol. of a l-amino-8-hydroxynaphthalene-3:6- or 4:6-disulfonic' acid, -1 mol. cyanuric chloride, 1 mol. of a yellow aminoazo-dyestuff and 1 mol. of a compound containing a primary or secondary amino-group and at least one alkyl-group bound to the nitrogen, and, if desired, treating the product thus obtained with a saponifying agent. 7 The following example illustrates the invention, the parts being by weight:-

Example 20 hard water, and, on the other hand, correspond to the general formula 621 parts of the dyestufi obtainable by coupling Rld 25 l %N C\ 2: HO No N I HO N=N- N -N 30 11 SOaIla z SO3Na- SOaNa z in which one 2 represents an SOaNa-group and the other 2 a hydrogen atom, y and 1c alkyl or alkoxy, R1 the radical of an amino compound-containing at least one alkyl-group bound to the nitrogen, and R2 the radical of a yellow aminoazo-dyestufl stands for hydrogen, alkyl radicals thalene series, R2 for hydrogen or alkyl, and R3 and R4 for aryl radicals of the benzene series. Such dyestuffs are obtained by causing to react with each other, in known manner and in suitable se- 45 quence. 1 mol. of the diazotized azo-dyestuif from or aryl radicals of the benzeneor of the naphheated to 85 C. and at this temperature the tol- It is suitable for dyeing various kinds of artifiuene sulfonic acid residue is split off by the adcial silk from regenerated cellulose, such as viscose dition of caustic soda solution. The dyestuff is or copper silk. salted out and dried. It dyes cotton in a dye- The following table gives a number of further bath made with either soft water or hard water, examples of dyestuffs obtainable in accordance 5 full green tints. The new dyestuff in the form with the invention and their properties:

Initial component Middle component Condensation product of 1 mol. cyanuric chloride with 1 mol. each of: 10

(l) l-amino-Shydroxy-naph- 1-methyl-3-amino-4- 1-amino-8-hydroxy- 4-amino-4J1ydr0xyazo- Monomethylamine.

thalene 3:6 dlsulfonic methoxy-benzene naphthalene-3:6-dibenzene-3-carboxylic acid sulfonic acid acid (2 Diethylamine. (3 Monomethylaniline. (4 4-emino-3-methyl-4-hy- Do. droxyezo-benzene-5- 15 carboxylic acid 25; 4-amino-azobenzene Do. 6 4-amino-3-methoxyazo- Do.

benzene-3'-sulfonic acid (7) 4 amino 4 hydroxy Do. (8) 4 23 2 11 d 6 D -am 0- y roxy- 0- 2 methylazo-benzene (9) 4 amino 4 hydroxy- 3- Do.

methylazo-bonzene (l0) 4 amino 4 hydroxy 2- Do.

methylazo-benzene (11) Do do 4 -amino 4' hydroxy 2- Do.

5-dimethyl-azobanzene (12) Do 1:4 dimethyl -2-am1- do 4-amino-4 -hydroxyaz0- D0. 25

nobenzene benizene 3 carboxylio am (13; Do... do do d Do. (14 Do. 2-amino-lz4-dimethdo do Monomethylamine.

oxybenzene (15) Do do do 3 amino-4-hydroxyazo- Monomethylanfline.

' benzene-3-carboxylic acid 30 of its sodium salt corresponds very probably with the formula.

OCH: HO HN-G\ /N COON a N=C H0 N=N N=N- 40' OH 40 OH: H

NaOaS SOgNB NBOIS S OzNa The formulas of some of the dyestuffs of the 45 above table are as follows:--

4 OCH: HO NC\ /N N=C 55 HO N=N N= CH: NaOaS SOzNB NaOflS S0,Na No. 6

Q R OCH; H0 N-G N /N SON I B =C no N=N- N= I 70 OH: NaOxS SO|NB OCH:

NaOIS S OgNB CH: HO

NaOaS SOaNB OOH: NaOzS- NaOsS SOzNa What we claim is:-

1. The green direct dyeing azo-dyestufis fast to light which are insensible in the dye-bath towards hard water and correspond to the general stand for radicals of the benzene series, which products constitute dark powders, are soluble in water to green solutions, and dye cotton or re- 5 generated cellulose green tints which are fast to formula light.

/RX 40 N-C R: z HO HN-C N 1 SOaNa- H S OaN8 S OINB z 50 NaSO 2. The green direct dyeing azo-dyestufis fast to light which areinsensible in the dye-bath to- 55 wards hard water and correspond to the general formula alkyl, R2 stands for a member of the group consisting of hydrogen, alkyl and aryl of the henzene and naphthalene series, and R3 and R4 in which Rrstands for alkyl, R2 stands for a member of the group consisting of hydrogen, alkyl and aryl of the benzene and naphthalene series, and 7 R3 and R4 stand for radicals of the benzene series dyebath towards hard water, and, on the other which products constitute dark powders, are 501- hand, corresponds to the general formula which product constitutes a dark powder, is soluble in Water to a, green solution, and dyes cotton or regenerated cellulose green tints which are fast to light.

15 uble in water to green solutions, and dye cotton or regenerated cellulose green tints which are fast to light.

3. The green, direct dyeing azo-dyestufi fast to light which, on the one hand, is insensible in the JOSEPH OTTO KAISER. 

